CN104812831B - There is the soft polypropylene composition of low normal hexane soluble substance - Google Patents
There is the soft polypropylene composition of low normal hexane soluble substance Download PDFInfo
- Publication number
- CN104812831B CN104812831B CN201380061121.0A CN201380061121A CN104812831B CN 104812831 B CN104812831 B CN 104812831B CN 201380061121 A CN201380061121 A CN 201380061121A CN 104812831 B CN104812831 B CN 104812831B
- Authority
- CN
- China
- Prior art keywords
- 10min
- weight
- polypropene composition
- pte
- thermoplastic elastomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention relates to a kind of two-phase mixture formed by the thermoplastic elastomer of polypropylene homopolymer and high molecular, it has processing characteristics, flexibility, the transparency and the optimum balance of low normal hexane extractable matter, so that resin being applied in order to possible in packaging for foodstuff.This material is the ideal material of injection molded article, in particular for producing the injection moulding flexible pipe of packaging for foodstuff application.This material can be used in cosmetics and pharmaceutical packing.
Description
Technical field
The present invention relates to a kind of novel soft polypropylene composition with low normal hexane soluble substance and the goods formed by it.
Background technology
Polymer is increasingly used in the application of different requirement.Concurrently there are disclosure satisfy that these requirements applied
The lasting exploration of particular composition.Owing to many polymer are directly or indirectly correlated with, demand becomes a kind of challenge.Such as,
In injection moulding field, particularly at injection moulding flexible pipe in the application such as food, cosmetics or drug packaging, acquisition is needed to add
Work performance and the optimum balance of appearance property, thus meet all adjustable requirements.
Multiphase system is known with its good impact property.Heterophasic propylene copolymers is well known in the art.Such many
Phase propylene copolymer comprises matrix, and matrix is Noblen or random copolymer of propylene, and elastomer copolymer disperses in the base.
Therefore polypropylene matrix comprises (subtly) scattered field trash, and field trash is not a part for matrix, and this field trash comprises bullet
Gonosome copolymer.Term field trash shows that matrix and field trash define different phases in heterophasic propylene copolymers, this field trash
At high resolution microscope, as visible in ultramicroscope or scanning force microscopy.
Summary of the invention
Therefore, it is an object of the invention to provide a kind of soft polymer compositions, this polymer composition has processing characteristics, softness
Property, the transparency, the optimum balance of low normal hexane extractable matter.
The present invention is the discovery that, it is provided that a kind of two-phase mixtures formed by the thermoplastic elastomer of polypropylene homopolymer and high molecular
Thing.
Therefore, the present invention relates to a kind of polypropene composition, polypropene composition have at least 85g/10min according to ISO
1133 melt flow rate (MFR)s MFR measured2(230 DEG C), described compositions includes two-phase mixture, described two-phase mixture by under
Row are formed:
A () polypropylene homopolymer matrix (PM), polypropylene homopolymer matrix (PM) has the root of at least 400g/10min
Melt flow rate (MFR) MFR measured according to ISO 11332(230 DEG C), and
B () acrylic thermoplastic elastomer (PTE), acrylic thermoplastic elastomer (PTE) is dispersed in polypropylene homopolymer matrix
(PM), in, there is melt flow rate (MFR) MFR measured according to ISO 1133 of at most 17g/10min2(230℃)。
The present invention be more particularly directed to a kind of polypropene composition, polypropene composition have at least 85g/10min according to ISO 1133
Melt flow rate (MFR) MFR measured2(230 DEG C), described compositions includes two-phase mixture, and described two-phase mixture is by following shape
Become:
A () polypropylene homopolymer matrix (PM), polypropylene homopolymer matrix (PM) has the root of at least 400g/10min
Melt flow rate (MFR) MFR measured according to ISO 11332(230 DEG C), and
B () acrylic thermoplastic elastomer (PTE), acrylic thermoplastic elastomer (PTE) is dispersed in polypropylene homopolymer matrix
(PM), in, there is melt flow rate (MFR) MFR measured according to ISO 1133 of at most 17g/10min2(230 DEG C),
Wherein said polypropene composition
C () includes the acrylic thermoplastic elastomer (PTE) of 25 weight % to 45 weight % based on whole polypropene compositions；
And/or
D () has the xylene soluble fraction (XCS) of 25 weight % to 50 weight %.
It was surprisingly found that according to the present invention, the thermoplastic elastomer (PTE) of polypropylene homopolymer and high molecular formed
Two-phase mixture has processing characteristics, flexibility, the transparency, the optimum balance of low normal hexane extractable matter, so that resin
Being applied in order to possible in packaging for foodstuff.This material is the ideal material of injection molded article, in particular for producing food bag
The injection moulding flexible pipe of dress application.This material can be used in cosmetics and pharmaceutical packing.
Limit the present invention in more detail below.
Polypropene composition
As it has been described above, the polypropene composition of the present invention is characterized with at a relatively high melt flow rate (MFR).It is therefore preferred that this
Bright polypropene composition has at least 85g/10min, preferably at least 90g/10min, more preferably at least 95g/10min, again
Melt flow rate (MFR) MFR measured according to ISO 1133 of more preferably at least 100g/10min2(230℃).Upper range is preferred
It is not more than 350g/10min, more preferably no more than 300g/10min, is even more preferably not more than 275g/10min, also will be more preferably
It is not more than 260g/10min.It should be appreciated that each higher limit can be combined with each lower limit, all these combinations all by
It is considered open and preferred, such as 85g/10min to 350g/10min, 85g/10min to 300g/10min, 85g/10min
To 275g/10min, 85g/10min to 260g/10min, 90g/10min to 350g/10min, 90g/10min to 300
G/10min, 90g/10min to 275g/10min, 90g/10min to 260g/10min, 95g/10min to 350g/10min,
95g/10min to 300g/10min, 95g/10min to 275g/10min, 95g/10min to 260g/10min, 100g/10min
To 350g/10min, 100g/10min to 300g/10min, 100g/10min to 275g/10m and 100g/10min extremely
260g/10min.In the range of particularly preferably 85g/10min to 350g/10min, more preferably at 85g/10min to 300
In the range of g/10min, even more preferably in the range of 85g/10min to 275g/10min, also will be more preferably at 95g/10min
To 260g/10min.
The further feature of the polypropene composition of the present invention is its amount of normal hexane soluble substance that is low or that reduced, the most still
So can keep the optimum balance of flow, rigidity, flexibility and the transparency.Preferably, normal hexane soluble substance is at Polypropylene compositions
Amount in thing is at most 6.8 weight %, preferably at most 6.5 weight %, more preferably up to 6.0 weight %, also will be more preferably
It is at most 5.8 weight %.In most preferred example, normal hexane soluble substance amount in polypropene composition is at most 5.0 weights
Amount %, the most at most 4.5 weight %.
Dimethylbenzene cold soluble substance (XCS) mark in polypropene composition is at least 20 weight %, preferably at least 25 weight %,
More preferably at least 27 weight %.Upper range is preferably not greater than 50 weight %, more preferably not more than 45 weight %, again
More preferably not more than 42 weight %.It should be appreciated that each higher limit can be combined with each lower limit, all these knots
Conjunction is considered as open and preferred, such as 20 weight % to 50 weight %, 20 weight % to 45 weight %, 20 weight %
To 42 weight %, 25 weight % to 50 weight %, 25 weight % to 45 weight %, 25 weight % to 42 weight %, 27 weights
Amount % to 50 weight %, 27 weight % to 45 weight % and 27 weight % are to 43 weight %.
The further feature of polypropene composition is the holding of its flexibility.Therefore preferred, polypropene composition has no more than
600MPa, more preferably less than 550MPa, 500MPa to be more preferably equal to or less than, even more preferably arrives at 200MPa
In the range of 550MPa, also will even more preferably in the range of 250MPa to 500MPa according to ISO 178 at 80x 10
x 4mm3Injection moulding sample on measure bending modulus.
Additionally, the polypropene composition of the present invention maintains good impact property (at 23 DEG C), impulsive force is at least 7
kJ/m2, preferably at least 15kJ/m2, more preferably at 7kJ/m2To 50kJ/m2In the range of, even more preferably at 7kJ/m2Arrive
30kJ/m2In the range of.
In a preferred embodiment, the polypropene composition of the present invention includes 25 weight % based on whole polypropene compositions
To 45 weight %, more preferably 27 weight % to 43 weight %, also will more preferably 25 weight % to 35 weight % acrylic heat
Plastics elastomer (PTE).
In a preferred embodiment, the polypropene composition of the present invention includes 55 weight % based on whole polypropene compositions
To 75 weight %, more preferably 57 weight % to 73 weight %, also will more preferably 65 weight % equal to the polypropylene of 75 weight %
Copolymer matrix (PM).
In a preferred embodiment, the polypropene composition of the present invention includes one or more of 0.1 weight % to 5 weight %
Additive defined below.
It is to be appreciated that in addition to polypropylene matrix PM mentioned above and thermoplastic elastomer PTE, according to the present invention's
Polypropene composition, particularly two-phase mixture can also contain other additives, but do not contain other polyolefin, based on entirely
Portion's polypropene composition, the content of additive for more than 5 weight %, more preferably no more than 3 weight %.
Statement two-phase system shows, the thermoplastic elastomer (PTE) of polypropylene homopolymer matrix (PM) and high molecular is not
Fusing, but define independent phase, this can such as be shown by such as the high-resolution such as ultramicroscope or scanning force microscopy
Micro mirror is observed.Preferably, the thermoplastic elastomer (PTE) of high molecular is formed in polypropylene homopolymer matrix (PM)
Field trash.In other words, the polypropene composition in the present invention is considered as heterogeneous system.
Independent component below be will be clarified in more detail.
Polypropylene homopolymer matrix (PM)
One important component of the polypropene composition of the present invention is polypropylene homopolymer matrix (PM).Table used in the present invention
State homopolymer to relate to substantially being made up of propylene units, i.e. by least 99.5 weight %, the third of more preferably at least 99.8 weight %
The polypropylene that alkene unit is formed.In a preferred embodiment, polypropylene homopolymer is only capable of propylene units detected.
Polypropylene homopolymer matrix (PM) according to the present invention has at least 450g/10min, preferably at least 550g/10min, more
Preferably at least 650g/10min, the most at least 750g/10min, also will more preferably at least 850g/10min according to ISO
1133 melt flow rate (MFR)s MFR measured2(230℃).Preferably upper range is not more than 1550g/10min, the most not quite
In 1450g/10min, or 1350g/10min.It should be appreciated that each higher limit can be combined with each lower limit, all
These combinations are considered as open and preferred, such as 450g/10min to 1550g/10min, 450g/10min to 1450
G/10min, 450g/10min to 1350g/10min, 550g/10min to 1550g/10min, 550g/10min are to 1450
G/10min, 550g/10min to 1350g/10min, 650g/10min to 1550g/10min, 650g/10min are to 1450
G/10min, 650g/10min to 1350g/10min, 750g/10min to 1550g/10min, 750g/10min are to 1450
G/10min, 750g/10min to 1350g/10min, 850g/10min to 1550g/10min, 850g/10min are to 1450
G/10min or 850g/10min to 1350g/10min.Particularly preferably 450g/10min to 1550g/10min scope
In, more preferably in the range of 550g/10min to 1450g/10min, even more preferably at 650g/10min to 1350g/10min
In the range of, also will more preferably in the range of 750g/10min to 1350g/10min, also will be even more preferably at 850g/10min
To 1350g/10min.
Preferably, polypropylene homopolymer matrix (PM) is visbreaking.Visbreaking may be in any known fashion
Carry out, but the present invention typically uses peroxide visbreaking dose to carry out chemistry visbreaking.Typical visbreaking agent is
2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (DHBP) is (such as with trade name Luperox 101 and Trigonox
101 sale), 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin-3 (DYBP) is (such as with trade name Luperox 130
With Trigonox 145 sale), cumyl peroxide (DCUP) is (such as with trade name Luperox DC and Perkadox
BC sells), di-t-butyl peroxide (DTBP) (is such as sold with trade name Trigonox B and Luperox Di),
T-butylcumylperoxide (BCUP) (is such as sold with trade name Trigonox T and Luperox 801), double (uncles
Butylperoxyisopropyl) benzene (DIPP) (such as selling with trade name Perkadox 14S and Luperox DC).This
The suitably amount of bright used peroxide is essentially well known by persons skilled in the art, it is possible to easily based on pending
The amount of polymer calculates.The amount of the most peroxide visbreaking dose is 0.005 weight % of amount based on the polymer used
To 0.5 weight %, more preferably 0.005 weight % is to 0.2 weight %.
Polypropylene homopolymer matrix (PM) has the highest degree of crystallinity.Therefore, the root in polypropylene homopolymer matrix (PM)
Dimethylbenzene cold soluble substance (XCS) mark measured according to ISO 16152 (25 DEG C) is at most 8 weight %, preferably at most 6 weight %,
More preferably up to 5 weight % and most preferably at most 4 weight %.Therefore, the cold soluble substance of dimethylbenzene (XCS) content is 0.5 weight
In the range of amount % to 8 weight %, be preferably in the range of 0.5 weight % to 6 weight %, more preferably 0.5 weight % is to 5 weight %
In the range of and most preferably 0.5 weight % to 4 weight % in the range of.
The melted temperature measured by differential scanning calorimetry (DSC) according to ISO 11,357 3 of polypropylene homopolymer matrix (PM)
Degree (Tm) be at least 140 DEG C, be preferably at least 145 DEG C, more preferably at least 150 DEG C, even more preferably at least 155 DEG C.On
Limit scope is preferably no greater than 170 DEG C, more preferably no more than 165 DEG C, to be also more preferably no more than 160 DEG C.It is to be appreciated that
Each higher limit can be combined with each lower limit, and all these combinations are considered as open and preferred, as 140 DEG C are arrived
170 DEG C, 145 DEG C to 165 DEG C, 150 DEG C to 165 DEG C, 155 DEG C to 165 DEG C, 150 DEG C to 160 DEG C and 155 DEG C are arrived
160℃。
Polypropylene homopolymer matrix (PM) according to the present invention can be commercially available, it is possible to use Ziegler-Natta catalyst or
Metallocene, preferably Ziegler-Natta catalyst produce.Polypropylene homopolymer matrix (PM) can be unimodal, bimodal
Or the Noblen of multimodal.Preferably, polypropylene homopolymer matrix (PM) is unimodal Noblen.
Unimodal Noblen is preferably generation in single stage process, as at slurry reactor (such as circulating reactor)
Single-reactor in.Polymerizing condition and response parameter are accurately controlled in the technical scope of this area.
The method may also comprise the prepolymerization using catalyst system and catalyzing, and catalyst system and catalyzing comprises Ziegler-Natta procatalyst, outside
Donor and optional promoter.
In prepolymerisation stage, the addition of other components is also possible.Therefore, hydrogen can be added by manner known in the art
Enter prepolymerisation stage, be controlled with the molecular weight to prepolymer.Additionally, antisatic additive may be used for preventing between particle
Each other absorption and the particle absorption to reactor wall.
Prepolymerization conditions and response parameter are accurately controlled in the technical scope of this area.
In order to obtain the polypropylene homopolymer of multimodal, multistage process can be used.It is preferably " circulation type-gas in this case
Phase " process, such as Borealis A/S, Denmark develops and is referred to asTechnology, such as such as EP 0 887 379,
WO 92/12182 WO 2004/000899, WO 2004/111095, WO 99/24478, WO 99/24479 or WO
Described in the patent documentation of 00/68315.
Another kind of slurry-the gas phase process being suitable for is Basell'sTechnique.
Polypropylene homopolymer for polypropylene homopolymer matrix (PM) is known in the art, and its example can be commercially available.
One preferred example is Borealis BorflowTM HL512FB。
Acrylic thermoplastic elastomer (PTE)
Another important component of polypropene composition is acrylic thermoplastic elastomer (PTE), its have most 17g/10min,
Preferably up to 14.5g/10min, more preferably up to 12g/10min, also will more preferably up to 10g/10min,
Many 8g/10min, also will even more preferably at most 6.5g/10min, even more preferably at most 5.0g/10min according to ISO 1133
Melt flow rate (MFR) MFR measured2(230℃).Thus, lower limit is preferably not less than 0.5g/10min, and more desirably not less than 1.0
G/10min and be even more preferably not less than 1.5g/10min.
It is to be appreciated that each higher limit can be combined with each lower limit, all these combinations are considered as open and preferred
, as 0.5g/10min to 17g/10min, 0.5g/10min to 14.5g/10min, 0.5g/10min to 12g/10min,
0.5g/10min to 10g/10min, 0.5g/10min to 8g/10min, 0.5g/10min to 6.5g/10min, 0.5g/10min
To 5g/10min, 1g/10min to 17g/10min, 1g/10min to 14.5g/10min, 1g/10min to 12g/10min,
1g/10min to 10g/10min, 1g/10min to 8g/10min, 1g/10min to 6.5g/10min, 1g/10min are to 5
G/10min, 1.5g/10min to 17g/10min, 1.5g/10min to 14.5g/10min, 1.5g/10min to 12g/10min,
1.5g/10min to 10g/10min, 1.5g/10min to 8g/10min, 1.5g/10min to 6.5g/10min, 1.5g/10min
To 5g/10min.In the range of particularly preferably 0.5g/10min to 17g/10min, it is more preferably 0.5g/10min to 14.5
In the range of g/10min, still more preferably from the range of 0.5g/10min to 12g/10min, 0.5g/10min to be more preferably
To 10g/10min, still more preferably from the range of 0.5g/10min to 6.5g/10min.There is melt described here
Flow rate MFR2Acrylic thermoplastic elastomer (PTE) be dispersed in polyacrylic polymer matrix (PM).
Moreover it is preferred that acrylic thermoplastic elastomer (PTE) has less than 920kg/m3, more preferably less than 910kg/m3、
Even more preferably at 800kg/m3To 920kg/m3In the range of, also will be more preferably at 840kg/m3To 880kg/m3In the range of with
And most preferably at 840kg/m3To less than 870kg/m3In the range of, as at 840kg/m3To 860kg/m3In the range of density.
Additionally, acrylic thermoplastic elastomer (PTE) has the advantages that degree of crystallinity is at a fairly low.Low crystallinity polymers has quite
Low melt temperature.Therefore, have less than 120 DEG C according to the acrylic thermoplastic elastomer (PTE) of the present invention, be preferably shorter than
110 DEG C, more preferably less than 100 DEG C, even more preferably 25 DEG C in the range of less than 120 DEG C, also will more preferably at 35 DEG C extremely
Melt temperature in the range of 110 DEG C.
Acrylic thermoplastic elastomer (PTE) is propylene copolymer, and propylene copolymer comprises propylene monomer units and comonomer list
Unit, comonomer unit is selected from ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene, it is preferable that copolymerization list
Body is selected from 1-octene and ethylene, and ethylene is more preferably.Preferably, the content of comonomer is that 6 weight % are to less than or equal to 25
Weight %, be preferably 7 weight % to 20 weight %, if 7.0 weight % are to 17.0 weight %.Particularly preferably ethylene copolymer
Content of monomer is 6 weight % to less than or equal to 25 weight %, and more preferably 7 weight % to 20 weight %, such as 7.0 weight %
To 17.0 weight %.
Preferably, produce in the presence of metalloscene catalyst according to the acrylic thermoplastic elastomer (PTE) of the present invention.
Acrylic thermoplastic elastomer (PTE) according to the present invention is known in the art.Typical commercial product is that some are high
The Vistamaxx polypropylene grade products of the Exxon Mobil of molecular weight, the Versify polypropylene grade products of Dow, Mitsui
Tafmer polypropylene and VLDPE grade products, and the TafmerBL polybutene grade products of Mitsui and Basell
Koattro polybutene grade products.
Polymer composition may comprise additive known in the art, such as antioxidant, acid scavenger, nucleator, anti
Agent, slipping agent and antistatic additive.The amount of the above-mentioned additive that typical compositions includes is less than 5 weight %, more preferably
Less than 3 weight %.If one or more additives are added into, preferably scope is as follows: 0.1 weight % to 5 weight %, 0.1
Weight % to 3 weight %, 0.3 weight % to 5 weight %, 0.3 weight % to 3 weight %, 0.5 weight % to 5 weight % or
0.5 weight % is to 3 weight %.
In a preferred embodiment of the invention, polypropene composition comprises the one or many of 0.1 weight % to 5 weight %
Plant selected from antiblocking agent (AB), slipping agent (SA), antioxidant, acid scavenger, nucleator or the additive of antistatic additive.
Preferably additive is antiblocking agent, slipping agent, antioxidant, acid scavenger and antistatic additive.More preferably antiblocking agent,
Slipping agent and antioxidant.
It is to be understood that, in the art, the interpolation of additive is the most common.Therefore, for technical staff personnel
It is open and it is well known that any one in the above-mentioned additive of above-mentioned amount may individually or be combined addition and gather with other additives
Any one in propylene compositions and combinations thereof.
The preparation of polypropene composition
Polyacrylic polymer in the present invention can be prepared by any suitable method known in the art, as by by poly-third
Polyamino alkenyl thing matrix (PM), acrylic thermoplastic elastomer (PTE) and optional additive directly mix, and such as, are squeezing
Go out in machine so that identical extruder may be used for the manufacture of finished product, or is blended in single blender or extrusion by pre-thawing
In machine.For mixing, conventional dispensing or mixing arrangement are used, such as class's background of cloth mixer, double roller rubber grinding machine, Buss
Co-kneader or double screw extruder.Other optional components, such as antiblocking agent and slipping agent, it is also possible to join in extruder.
Goods
The present invention is directed not only to the polypropene composition of the present invention itself, and relates to the system of the polypropene composition comprising the present invention
Product.Therefore, goods include at least 70 weight %, and if 70 weight % are to 99 weight %, or 70 weight % are to 100 weight %,
Preferably at least 80 weight %, if 80 weight % are to 99 weight %, or 80 weight % are to 100 weight %, and more preferably at least 95
Weight %, such as 95 weight % to 99 weight %, or 95 weight % are to the polypropene composition of 100 weight %, also will be more preferably
It is made up of the polypropene composition of the present invention.
Article according to the invention is injection molding goods, particularly thin-gage goods, such as light-wall pipe.Term " thin-walled " should be excellent
Choosing represent thickness less than 2mm, more preferably in the range of 0.05mm to 2.00mm, even more preferably at 0.10mm to 1.70
In the range of mm, also will more preferably in the range of 0.18mm to 1.20mm, even more preferably from 0.25mm to 1.00mm model
In enclosing, as in the range of 0.30mm to 0.60mm.
Detailed description of the invention
To be more fully described the present invention by examples provided below now.
Example
Method of testing and definition
It is to be appreciated that term " number x to number y " refers to " number x is to less than or equal to number y " in whole application.
MFR2(230 DEG C) are measured according to ISO 1133 (230 DEG C, 2.16kg loads).
MFR2(190 DEG C) are measured according to ISO 1133 (190 DEG C, 2.16kg loads).
The cold soluble substance of dimethylbenzene (XCS, weight %) content: according to ISO 16152；The first edition；2005-07-01 gets off at 25 DEG C
Measure.
The co-monomer content of acrylic thermoplastic elastomer (PTE) measures according to ASTM D 3900.
The co-monomer content of matrix (M), particularly ethylene contents are by using13The Fourier of C-NMR spectrographic method calibration
Transform infrared spectroscopy method (FTIR) is measured.When the ethylene contents measured in polypropylene, sample thin film (thickness is about 250 μm)
Standby by hot pressing.Propylene-ethylene copolymers is at 720cm-1And 733cm-1The peak area of the absworption peak at place is to pass through Perkin
Elmer FTIR 1600 spectrophotometer.Propene-1-butene copolymer is at 767cm-1Locate evaluated.Method is passed through13C-NMR
Measured ethylene contents data calibration.Referring also to " IR-Spektroskopie f ü r Anwender "；WILEY-VCH, 1997 Hes
“Validierung in der Analytik”,WILEY-VCH,1997。
Bending modulus: bending modulus is prepared according to ISO 294-1:1996 according to ISO 178 three-point bend test method, use
The injection moulding sample of 80x10x4mm measures.
Stretch modulus: stretch modulus according to ISO 527-1 (crosshead speed is 1mm/min) at 23 DEG C, according to ISO 527-2
(1B) the injection moulding sample (dog bone, thickness is 4mm) prepared according to EN ISO 1873-2 is used to measure.
Impact test: Sha Erpi notch impact strength is according to ISO 179/1eA, at 23 DEG C, use EN ISO 1873-2
(80x10x4mm) the injection moulding test sample described by measures.
Hexane extractables level mark according to FDA method (federal registration table, title 21, the 1st chapter, the 177th part, 1520
Section, s.Annex B) preparation on the monolayer cast film production line that temperature is 20 DEG C that melt temperature is 220 DEG C and chill roll
Thickness is to measure in the casting films of 100 μm.Extraction carries out 30min at a temperature of 50 DEG C.
Mist degree: mist degree is using the melt temperature of 200 DEG C to be injected into according to ASTM D 1003-07 according to EN ISO 1873-2
The 60x60x0.5mm of type3Measure on substrate.
Transparency: transparency is noted at the melt temperature using 200 DEG C according to EN ISO 1873-2 according to ASTM D1003-00
Penetrate the 60x60x0.5mm of molding3Measure on substrate.
Density: measure according to ISO 1183-1 method A (2004).Sample is prepared by the pressure according to ISO 1872-2:2007
Mould and carry out.
Melt temperature Tm, crystallization temperature Tcr and degree of crystallinity: use Mettler TA820 differential scanning calorimetry (DSC) to 3 ± 0.5
Mg sample measures.Crystallization curve and melting curve 10 DEG C/min between 30 DEG C to 225 DEG C cools down and heat scan
During obtain.Melt temperature and crystallization temperature take the peak value of endothermic curve and exotherm.Degree of crystallinity by and be fully crystallized
The contrast of polyacrylic heat of fusion calculates, i.e. 209J/g (ISO 11357-3).
Experimental section:
Table 1: compositions
* be up to 100 weight % remainder be typical additive, such as antioxidant.
IE2 is particularly preferred.
HL512FB is the commodity Noblen of Borealis AG, and it has the MFR of 1200g/10min2(230℃)、2.8
The XCS of weight %, melt temperature Tm of 158 DEG C.
Vistamax 6102 is the commodity ethylene propylene copolymer VISTAMAXX 6102 of Exxon Mobil, and it has 3.0
The MFR of g/10min2Shore A measured according to ASTM D2240 of (230 DEG C), the ethylene contents of 16.0 weight % and 67
Hardness.
Engage 8401 is the commodity ethylene-octene copolymer of Dow Chemical Company, and it has 30g/10min's
MFR2(190 DEG C), the isooctane content of 31 weight % and 0.885g/cm3According to ASTM D792 measure density.
Versify DE4301 is the elastomer of Dow Chemical Company, and it has 25g/10min's
MFR2(230 DEG C), 0.868g/cm according to ASTM D792 measure density and 84 according to ASTM D2240 measure
Shore A hardness.
Table 2 performance
| CE 1 | CE2 | CE3 | IE 1 | IE 2 | ||
| MFR2(230℃) | [g/10min] | 232 | 662 | 417 | 136 | 208 |
| MFR2(190℃) | [g/10min] | 88 | 203 | - | 52 | 70 |
| Hexane solubles | [weight %] | 7.3 | - | - | 5.6 | 4.4 |
| XCS | [weight %] | 37 | 11 | 20 | 40 | 30 |
| Stretch modulus | [MPa] | 517 | 1133 | 842 | 385 | - |
| Bending modulus | [MPa] | 465 | 1101 | 788 | 370 | 484 |
| Impact | [kJ/m2] | 7.7 | 1.7 | 3.3 | 28 | 7.7 |
| Mist degree | [%] | 41 | - | - | 41 | 41 |
| Transparency | [%] | 94 | - | - | 92 | 92 |
The present invention is a kind of two-phase mixture formed by the thermoplastic elastomer of polypropylene homopolymer and high molecular.Current combination
Thing provides low hexane extractable, can form the optimum balance of flow, rigidity, flexibility and the transparency simultaneously.This property
Energy distribution is the important parameter of soft injection moulding pipe, can be used for packaging for foodstuff application.This application can be to cosmetics and medicine
Application extension.
Claims (13)
1. a polypropene composition, have at least 85g/10min according to ISO 1133 230 DEG C measure melt flows
Speed MFR2, described compositions includes that two-phase mixture, described two-phase mixture are formed by following:
A () polypropylene homopolymer matrix (PM), described polypropylene homopolymer matrix (PM) has at least 400g/10min
According to ISO 1133 230 DEG C measure melt flow rate (MFR)s MFR2, and
B () acrylic thermoplastic elastomer (PTE), described acrylic thermoplastic elastomer (PTE) is dispersed in described polypropylene and gathers
In compound matrix (PM), have at most 17g/10min according to ISO 1133 230 DEG C measure melt flow rate (MFR)s
MFR2,
Wherein said polypropene composition
C () includes the described acrylic thermoplastic elastomer of 27 weight % to 43 weight % based on whole polypropene compositions
(PTE)。
Polypropene composition the most according to claim 1, wherein said compositions has in the curtain coating that thickness is 100 μm
The normal hexane solubles content of at most 6.8 weight % measured on film, extracts at a temperature of 50 DEG C.
Polypropene composition the most according to claim 1 and 2, wherein said compositions has 25 weight % to 50 weights
The xylene soluble fraction (XCS) of amount %.
Polypropene composition the most according to claim 1 and 2, wherein said compositions comprises 55 weight % to 75 weights
The polypropylene homopolymer matrix (PM) of amount %.
Polypropene composition the most according to claim 1 and 2, wherein said acrylic thermoplastic elastomer (PTE) has
Have at most 6.5g/10min according to ISO 1133 230 DEG C measure melt flow rate (MFR)s MFR2。
Polypropene composition the most according to claim 1 and 2, wherein said acrylic thermoplastic elastomer (PTE) is wrapped
Containing propylene monomer units with selected from ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene and the comonomer unit of 1-octene.
Polypropene composition the most according to claim 1 and 2, wherein said acrylic thermoplastic elastomer (PTE) has
Have in 6 weight % to less than or equal to the co-monomer content in the range of 25 weight %.
Polypropene composition the most according to claim 7, wherein said acrylic thermoplastic elastomer (PTE) has 6
Weight % is to less than or equal to the ethylene comonomer content in the range of 25 weight %.
Polypropene composition the most according to claim 1 and 2, wherein said polypropylene homopolymer matrix (PM) has
At most 10 weight % according to ISO 16152 25 DEG C measure dimethylbenzene cold soluble substance (XCS) marks.
Polypropene composition the most according to claim 1 and 2, wherein said polypropylene homopolymer matrix (PM) has
Unimodal molecular weight is had to be distributed.
11. 1 kinds for the method preparing a described polypropene composition in aforementioned claim, described method include with
Lower step:
By described polypropylene homopolymer matrix (PM), described acrylic thermoplastic elastomer (PTE) and optional one or more
Additive is extruded in an extruder.
12. 1 kinds of goods, including polypropene composition according to any one of claim 1 to 10.
13. according to the goods described in claim 12, for injection molded article.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12194871.5A EP2738216B1 (en) | 2012-11-29 | 2012-11-29 | Soft polypropylene composition with low n-hexane solubles |
| EP12194871.5 | 2012-11-29 | ||
| PCT/EP2013/075016 WO2014083131A1 (en) | 2012-11-29 | 2013-11-28 | Soft polypropylene composition with low n-hexane solubles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104812831A CN104812831A (en) | 2015-07-29 |
| CN104812831B true CN104812831B (en) | 2016-10-12 |
Family
ID=47227700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380061121.0A Expired - Fee Related CN104812831B (en) | 2012-11-29 | 2013-11-28 | There is the soft polypropylene composition of low normal hexane soluble substance |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2738216B1 (en) |
| CN (1) | CN104812831B (en) |
| AU (1) | AU2013351170B2 (en) |
| ES (1) | ES2531469T3 (en) |
| PL (1) | PL2738216T3 (en) |
| WO (1) | WO2014083131A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013141398A1 (en) * | 2012-03-19 | 2013-09-26 | 住友化学株式会社 | Polypropylene resin composition and molded body |
| RS63924B1 (en) | 2019-07-16 | 2023-02-28 | Constantia Teich Gmbh | Composite material for producing lids and lids made therefrom |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597096A (en) * | 2009-11-16 | 2012-07-18 | 博里利斯股份公司 | Melt blown fibers of polypropylene compositions |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI86867C (en) | 1990-12-28 | 1992-10-26 | Neste Oy | FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN |
| FI111848B (en) | 1997-06-24 | 2003-09-30 | Borealis Tech Oy | Process and equipment for the preparation of homopolymers and copolymers of propylene |
| JPH1180298A (en) * | 1997-08-29 | 1999-03-26 | Toyota Motor Corp | Polypropylene/propylene-ethylene copolymer composition and preparation thereof |
| FI980342A0 (en) | 1997-11-07 | 1998-02-13 | Borealis As | Polymerroer och -roerkopplingar |
| FI974175A (en) | 1997-11-07 | 1999-05-08 | Borealis As | Process for producing polypropylene |
| FI991057A0 (en) | 1999-05-07 | 1999-05-07 | Borealis As | High stiffness propylene polymers and process for their preparation |
| US20060052541A1 (en) | 2002-06-25 | 2006-03-09 | Erling Hagen | Polyolefin with improved scratch resistance and process for producing the same |
| EP1484343A1 (en) | 2003-06-06 | 2004-12-08 | Universiteit Twente | Process for the catalytic polymerization of olefins, a reactor system and its use in the same process |
| US20100125114A1 (en) * | 2008-11-14 | 2010-05-20 | Williams Michael G | Propylene-Based Film Compositions |
| EP2558627B1 (en) * | 2010-04-12 | 2018-10-03 | Nicolon Corporation doing business as Tencate Geosynthetics North America | Polypropylene yarn having increased young's modulus and method of making same |
| EP2397517B1 (en) * | 2010-06-16 | 2012-12-26 | Borealis AG | Propylene polymer compositions having superior hexane extractables/impact balance |
-
2012
- 2012-11-29 PL PL12194871T patent/PL2738216T3/en unknown
- 2012-11-29 ES ES12194871.5T patent/ES2531469T3/en active Active
- 2012-11-29 EP EP12194871.5A patent/EP2738216B1/en active Active
-
2013
- 2013-11-28 WO PCT/EP2013/075016 patent/WO2014083131A1/en active Application Filing
- 2013-11-28 AU AU2013351170A patent/AU2013351170B2/en not_active Ceased
- 2013-11-28 CN CN201380061121.0A patent/CN104812831B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597096A (en) * | 2009-11-16 | 2012-07-18 | 博里利斯股份公司 | Melt blown fibers of polypropylene compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2738216A1 (en) | 2014-06-04 |
| CN104812831A (en) | 2015-07-29 |
| WO2014083131A1 (en) | 2014-06-05 |
| EP2738216B1 (en) | 2015-01-07 |
| ES2531469T3 (en) | 2015-03-16 |
| PL2738216T3 (en) | 2015-08-31 |
| AU2013351170B2 (en) | 2015-12-17 |
| AU2013351170A1 (en) | 2015-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103998477B (en) | For injection molded article or the propylene copolymer of thin film | |
| US10059785B2 (en) | Polypropylene-polyethylene composition with improved flowability | |
| CN102112541B (en) | Composition based on polypropylene compounds with styrenic based elastomers | |
| US8173747B2 (en) | Sterilisable and tough impact polypropylene composition | |
| CN102089378B (en) | Heterophasic polymer composition providing high sealing strength | |
| CN103890078B (en) | Polypropylene blend with improved balance between sit and melting point | |
| CN101490165B (en) | Use of polypropylene composition | |
| EP2831169A1 (en) | Soft polypropylene with improved optical properties | |
| CN102355994A (en) | Multilayer propylene resin sheet and packaging material for heating treatment comprising same | |
| JP6006887B2 (en) | Random propylene copolymer for bottles with good optical properties | |
| JP6005174B2 (en) | Increased production in film extrusion | |
| WO2014090818A1 (en) | Extrusion blow molded bottles | |
| JP5255433B2 (en) | Polypropylene resin composition, molded body, sheet, and container | |
| JP7549684B2 (en) | Propylene-based polymer compositions and their uses | |
| JP2015535025A (en) | Random propylene copolymer for bottles with good optical properties and low hexane content | |
| CN104812831B (en) | There is the soft polypropylene composition of low normal hexane soluble substance | |
| CN109642065A (en) | Rigid propylene compositions with good dimensional stability and excellent surface appearance | |
| TW200526734A (en) | Polypropylene-base molded article and container | |
| CN108137882A (en) | Including the syndiotactic polypropylene manufactured by single-site catalysts the and polyolefin blends of polyethylene, the technique and product manufactured by these blends | |
| JP4393772B2 (en) | Medical container | |
| EP3436521B1 (en) | Low crystalline polymer compositions prepared in a dual reactor | |
| KR100736290B1 (en) | Medical Container | |
| CN101484522A (en) | Polyolefin composition suitable for bottles with high-impact strength and transparency | |
| CN109642062A (en) | Polyolefin blends, technique including the isotactic polypropylene and polyethylene that are manufactured single-site catalysts and the product made of these blends | |
| CN104245821A (en) | Soft bottles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161012 Termination date: 20191128 |